Compounds and organic light emitting devices comprising the same

Abstract

The present invention provides novel compounds and organic light emitting devices comprising the same.

Description

Technical Field

[0001] Cross-reference with related applications

[0002] This application claims priority based on Korean Patent Application No. 10-2021-0056813, dated April 30, 2021, the entire contents of which are disclosed in the document and are incorporated herein by reference.

[0003] This invention relates to novel compounds and organic light-emitting devices containing the same. Background Technology

[0004] Organic light emission typically refers to the phenomenon of converting electrical energy into light energy using organic materials. Organic light-emitting devices (OLEDs) utilizing organic light emission exhibit wide viewing angles, excellent contrast ratios, fast response times, and superior brightness, driving voltage, and response speed characteristics, thus attracting extensive research.

[0005] Organic light-emitting devices (OLEDs) typically have a structure comprising an anode and a cathode, and an organic layer located between the anode and cathode. To improve the efficiency and stability of OLEDs, the organic layer is often formed by a multilayer structure composed of different materials, such as a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In such an OLED structure, if a voltage is applied between the two electrodes, holes are injected into the organic layer from the anode, and electrons are injected into the organic layer from the cathode. When the injected holes and electrons meet, they form excitons, which emit light when they re-enter the ground state.

[0006] For organic materials used in organic light-emitting devices as described above, there is a continuous need to develop new materials.

[0007] Existing technical documents

[0008] Patent documents

[0009] (Patent Document 0001) Korean Patent Publication No. 10-2000-0051826 Summary of the Invention

[0010] Technical issues

[0011] This invention relates to novel compounds and organic light emitters containing the same.

[0012] Solution to the problem

[0013] The present invention provides compounds represented by the following chemical formula 1.

[0014] [Chemical Formula 1]

[0015]

[0016] In the above chemical formula 1,

[0017] A is a benzene or naphthalene ring fused with an adjacent ring.

[0018] L1 to L3 are each independently C that is directly bonded, substituted, or unsubstituted. 6-60 Alpha-aryl

[0019] Ar1 and Ar2 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Mixed aromatics,

[0020] Y is either O or S.

[0021] X1 to X4 are each independently N or C(R2), and at least one of X1 to X4 is N.

[0022] R1 and R2 are each independently hydrogen; deuterium; substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Mixed aromatics,

[0023] When A is a benzene ring, n is an integer from 1 to 5; when A is a naphthalene ring, n is an integer from 1 to 7.

[0024] In addition, the present invention provides an organic light-emitting device, comprising: a first electrode, a second electrode disposed opposite to the first electrode, and an organic layer of one or more disposed between the first electrode and the second electrode, wherein one or more of the organic layers comprises a compound represented by the above chemical formula 1.

[0025] Invention Effects

[0026] The compounds represented by the above-described chemical formula 1 can be used as materials for the organic layer of organic light-emitting devices, thereby achieving improved efficiency, lower driving voltage, and / or improved lifetime characteristics in organic light-emitting devices. In particular, the compounds represented by the above-described chemical formula 1 can be used as materials for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection. Attached Figure Description

[0027] Figure 1 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.

[0028] Figure 2The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, an electron injection and transport layer 8, and a cathode 4. Detailed Implementation

[0029] The invention will now be described in more detail to aid in understanding.

[0030] In this instruction manual, or This indicates a bond that is linked to other substituents.

[0031] In this specification, the term "substituted or unsubstituted" refers to a substituent selected from deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thio group; aryl thio group; alkyl sulfonyl group; aryl sulfonyl group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; arylenyl group; alkylaryl group; alkylamine group; aralkylamine group; heteroarylamine group; arylamine group; arylphosphine group; or one or more heterocyclic groups containing one or more N, O, and S atoms, or a substituent formed by linking two or more substituents exemplified above. For example, "a substituent formed by linking two or more substituents" can be biphenyl. That is, biphenyl can be aryl, or it can be interpreted as a substituent formed by linking two phenyl groups.

[0032] In this specification, the number of carbon atoms in the carbonyl group is not particularly limited, but it is preferred to have 1 to 40 carbon atoms. Specifically, it can be a group with the following structure, but is not limited thereto.

[0033]

[0034] In this specification, the oxygen atom in the ester group may be replaced by a straight-chain, branched, or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a group with the following structural formula, but is not limited thereto.

[0035]

[0036] In this specification, the number of carbon atoms in the imide group is not particularly limited, but it is preferred to have 1 to 25 carbon atoms. Specifically, it can be a group with the following structure, but is not limited thereto.

[0037]

[0038] In this specification, silanes specifically include trimethylsilane, triethylsilane, tert-butyldimethylsilane, vinyldimethylsilane, propyldimethylsilane, triphenylsilane, diphenylsilane, phenylsilane, etc., but are not limited to these.

[0039] In this specification, boron groups specifically include trimethylboronyl, triethylboronyl, tert-butyldimethylboronyl, triphenylboronyl, phenylboronyl, etc., but are not limited to these.

[0040] Examples of halogen groups in this specification include fluorine, chlorine, bromine, or iodine.

[0041] In this specification, the alkyl group can be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to yet another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc., but are not limited to these.

[0042] In this specification, the alkenyl group can be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to yet another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, styryl, styryl, etc., but are not limited to these.

[0043] In this specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group with 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., are used, but are not limited to these.

[0044] In this specification, the aryl group is not particularly limited, but is preferably an aryl group with 6 to 60 carbon atoms, and can be a monocyclic aryl or polycyclic aryl. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to another embodiment, the aryl group has 6 to 20 carbon atoms. Regarding the aforementioned aryl group, as a monocyclic aryl group, it can be phenyl, biphenyl, terphenyl, etc., but is not limited to these. As the aforementioned polycyclic aryl group, it can be naphthyl, anthraceneyl, phenanthryl, pyrene, peryl, thionyl, fluoreneyl, etc., but is not limited to these.

[0045] In this specification, the fluorene group can be substituted, and two substituents can combine with each other to form a spirostructure. When the fluorene group is substituted as described above, it can be used to... Etc. But it is not limited to this.

[0046] In this specification, a heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as heteroelements. The number of carbon atoms is not particularly limited, but is preferably 2 to 60. Examples of heterocyclic groups include thiophene, furanyl, pyrrole, imidazolyl, and thiazolyl. azole group, Diazolyl, Triazolyl, Pyridyl, Bipyridyl, Pyrimidinyl, Triazinyl, Acridineyl, Pyridazinyl, Quinolinyl, Quinazolinyl, Quinoxalinyl, Phtharazineyl, Pyridopyrimidinyl, Pyridopyrazinyl, Pyrazenopyrazinyl, Isoquinolinyl, Indoleyl, Carbazoleyl, Benzo[] Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazole, benzothiophene, dibenzothiophene, benzofuranyl, phenanthroline, iso Azolyl, thiadiazolyl, phenthiazinyl, and dibenzofuranyl groups, but not limited to these.

[0047] In this specification, the aryl groups in aralkyl, aryl-alkenyl, alkylaryl, and arylamine are the same as those exemplified above. In this specification, the alkyl groups in aralkyl, alkylaryl, and alkylamine are the same as those exemplified above. In this specification, the heteroaryl groups in heteroarylamines are subject to the above description of heterocyclic groups. In this specification, the alkenyl groups in aryl-alkenyl are the same as those exemplified above. In this specification, arylene is a divalent group; otherwise, the above description of aryl groups applies. In this specification, heteroarylene is a divalent group; otherwise, the above description of heterocyclic groups applies. In this specification, the hydrocarbon ring is not a monovalent group but is formed by the combination of two substituents; otherwise, the above description of aryl or cycloalkyl groups applies. In this specification, the heterocycle is not a monovalent group but is formed by the combination of two substituents; otherwise, the above description of heterocyclic groups applies.

[0048] (Compound)

[0049] The present invention provides compounds represented by the above chemical formula 1.

[0050] Preferably, the above chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-4.

[0051] [Chemical Formula 1-1]

[0052]

[0053] [Chemical Formula 1-2]

[0054]

[0055] [Chemical Formulas 1-3]

[0056]

[0057] [Chemical Formulas 1-4]

[0058]

[0059] In the above chemical formulas 1-1 to 1-4,

[0060] L1 to L3, Ar1, Ar2, Y, and X1 to X4 are defined in the same way as above.

[0061] Preferably, L1 to L3 are each independently a direct bond, a phenylene group, or a biphenyl diene group.

[0062] Preferably, Ar1 and Ar2 are each independently phenyl, biphenyl, naphthyl, dibenzofuranyl or dibenzothiophene.

[0063] Preferably, X1 to X4 are each independently N or C(R2), and any one of X1 to X4 is N.

[0064] Preferably, R1 is each independently hydrogen or deuterium, and R2 is each independently hydrogen, deuterium, or phenyl.

[0065] Representative examples of compounds represented by the above chemical formula 1 are shown below:

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075] In addition, the present invention provides a method for manufacturing the compound represented by the above chemical formula 1 as shown in reaction formulas 1-1 and 1-2 below.

[0076] [Reaction Formula 1-1]

[0077]

[0078] [Reaction 1-2]

[0079]

[0080] In the above reaction formulas 1-1 and 1-2, everything except Z is the same as defined above, where Z is a halogen, preferably bromine or chlorine.

[0081] (Organic light-emitting devices)

[0082] Furthermore, the present invention provides an organic light-emitting device comprising a compound represented by the above-described chemical formula 1. As an example, the present invention provides an organic light-emitting device comprising: a first electrode, a second electrode disposed opposite to the first electrode, and one or more organic layers disposed between the first electrode and the second electrode, wherein one or more of the organic layers comprises a compound represented by the above-described chemical formula 1.

[0083] The organic layer of the organic light-emitting device of the present invention can be formed as a single layer or as a multilayer structure with two or more organic layers stacked on top of each other. For example, the organic light-emitting device of the present invention can have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, and an electron injection layer as organic layers. However, the structure of the organic light-emitting device is not limited to this and may include fewer organic layers.

[0084] In addition, the aforementioned organic layer may include a hole transport layer, a hole injection layer, or a layer that performs both hole transport and hole injection simultaneously, and the aforementioned hole transport layer, hole injection layer, or layer that performs both hole transport and hole injection simultaneously may contain a compound represented by the aforementioned chemical formula 1.

[0085] Additionally, the aforementioned organic layer may include an electron blocking layer, which is present between the anode and the light-emitting layer. Preferably, the electron blocking layer is attached to the anode side of the light-emitting layer. The electron blocking layer improves the efficiency of the organic light-emitting device by preventing electrons injected from the cathode from recombinizing in the light-emitting layer and thus preventing their transfer to the anode side. The electron blocking layer may contain a compound represented by the aforementioned chemical formula 1.

[0086] Furthermore, the aforementioned organic layer may include a light-emitting layer, which may contain a compound represented by the aforementioned chemical formula 1. In particular, the compound according to the present invention can be used as the host of the light-emitting layer.

[0087] In addition, the aforementioned organic layer may include an electron transport layer, an electron injection layer, or an electron injection and transport layer, wherein the aforementioned electron transport layer, electron injection layer, or electron injection and transport layer may contain a compound represented by the aforementioned chemical formula 1.

[0088] In addition, the aforementioned organic layer may include a light-emitting layer or an electron-blocking layer, which may contain a compound represented by the aforementioned chemical formula 1.

[0089] Furthermore, the organic light-emitting device according to the present invention can be a structure (normal type) in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. Additionally, the organic light-emitting device according to the present invention can be a reverse structure (inverted type) in which a cathode, one or more organic layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light-emitting device according to an embodiment of the present invention is illustrated below. Figure 1 and 2 middle.

[0090] Figure 1The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In the structure described above, the compound represented by the above chemical formula 1 may be included in the light-emitting layer.

[0091] Figure 2 The illustration shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, an electron injection and transport layer 8, and a cathode 4. In the structure described above, the compound represented by the above-described chemical formula 1 may be included in the light-emitting layer or the electron blocking layer.

[0092] The organic light-emitting device according to the present invention, except that one or more of the organic layers contain a compound represented by the above-described chemical formula 1, can be manufactured using materials and methods known in the art. Furthermore, when the organic light-emitting device comprises a plurality of organic layers, the organic layers can be formed from the same substance or different substances.

[0093] For example, the organic light-emitting device according to the present invention can be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. This can be achieved by: depositing a metal or a conductive metal oxide or alloy thereof onto the substrate using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation to form an anode; then forming an organic layer comprising a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer on the anode; and finally depositing a material suitable for use as a cathode onto the organic layer. Alternatively, the organic light-emitting device can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material onto the substrate.

[0094] Furthermore, the compound represented by the above chemical formula 1 can be used to form an organic layer in the manufacture of organic light-emitting devices not only by vacuum evaporation but also by solution coating. Here, solution coating refers to methods such as spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, and roller coating, but is not limited to these.

[0095] In addition to these methods, organic light-emitting devices can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003 / 012890). However, the manufacturing method is not limited to these methods.

[0096] As an example, the first electrode is the anode and the second electrode is the cathode, or the first electrode is the cathode and the second electrode is the anode.

[0097] As the aforementioned anode material, a material with a high work function is preferred in order to facilitate the injection of holes into the organic layer. Specific examples of the aforementioned anode materials include metals such as vanadium, chromium, copper, zinc, and gold, or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylidene-1,2-dioxo)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited to these.

[0098] As the cathode material described above, a material with a low work function is generally preferred in order to facilitate the injection of electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or their alloys; multilayer structures such as LiF / Al or LiO2 / Al, etc., but are not limited to these.

[0099] The aforementioned hole injection layer is a layer that injects holes from the electrode. Preferably, the hole injection material is a compound that possesses the ability to transport holes, the effect of injecting holes from the anode, excellent hole injection performance for the light-emitting layer or light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the electron injection layer or electron injection material, and exhibits excellent thin film formation capability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injection material is between that of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injection materials include, but are not limited to, metalloporphyrins, oligothiophenes, arylamine-based organic compounds, hexanitrile hexaazabenzophenanthrene-based organic compounds, quinacridone-based organic compounds, perylene-based organic compounds, anthraquinones, and conductive polymers based on polyaniline and polythiophene.

[0100] The aforementioned hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light-emitting layer. The hole transport material is a substance capable of receiving holes from the anode or hole injection layer and transferring them to the light-emitting layer; substances with high hole mobility are suitable. Specific examples include aryl amine-based organic compounds, conductive polymers, and block copolymers that simultaneously contain conjugated and non-conjugated portions, but are not limited to these.

[0101] The aforementioned electron blocking layer refers to a layer formed on the aforementioned hole transport layer, preferably disposed in contact with the light-emitting layer, which improves the probability of hole-electron binding by adjusting the hole mobility and preventing excessive electron migration, thereby improving the efficiency of the organic light-emitting device. The aforementioned electron blocking layer contains an electron blocking material. Examples of such an electron blocking material include compounds represented by the aforementioned chemical formula 1, and further examples include arylamine-based organic compounds, but it is not limited to these.

[0102] The aforementioned luminescent material is capable of receiving holes and electrons from the hole transport layer and electron transport layer, respectively, and combining them to emit light in the visible light region. Preferably, it is a material with high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxyquinoline aluminum complex (Alq3); carbazole compounds; diluted styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; and benzo[…]. Compounds including azoles, benzothiazoles and benzimidazoles; poly(p-phenylenevinylene) (PPV) polymers; spiro compounds; polyfluorene, fluorene, etc., but not limited to these.

[0103] The aforementioned luminescent layer may comprise a host material and a dopant material. The host material may be an aromatic fused-ring derivative or a heterocyclic compound. Specifically, aromatic fused-ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentanebenzene derivatives, phenanthrene compounds, and fluoranthene compounds; heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, and pyrimidine derivatives, but are not limited to these.

[0104] As dopant materials, there are aromatic amine derivatives, styrene amine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives are aromatic fused-ring derivatives having substituted or unsubstituted aryl amino groups, such as pyrene, anthracene, benzo[a]pyrene, etc., having aryl amino groups. Styrene amine compounds are compounds in which at least one aryl vinyl group is substituted on a substituted or unsubstituted aryl amine, and is substituted or unsubstituted by one or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups. Specifically, there are styrene amines, styrene diamines, styrene triamines, styrene tetraamines, etc., but they are not limited to these. In addition, as metal complexes, there are iridium complexes, platinum complexes, etc., but they are not limited to these.

[0105] The aforementioned electron transport layer is the layer that receives electrons from the electron injection layer and transports them to the light-emitting layer. The electron transport material is one that can effectively receive electrons from the cathode and transfer them to the light-emitting layer; materials with high electron mobility are suitable. Specific examples include Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavonoid-metal complexes, etc., but are not limited to these. The electron transport layer can be used with any desired cathode material as used in the prior art. In particular, examples of suitable cathode materials are common materials with low work functions and accompanied by an aluminum or silver layer. Specifically, these are cesium, barium, calcium, ytterbium, and samarium, each accompanied by an aluminum or silver layer.

[0106] The aforementioned electron injection layer is a layer that injects electrons from the electrode. Preferably, compounds are those that possess electron transport capabilities, effectively inject electrons from the cathode, exhibit excellent electron injection performance for the light-emitting layer or material, prevent excitons generated in the light-emitting layer from migrating to the hole injection layer, and demonstrate excellent thin-film formation ability. Specifically, these include fluorenone, anthraquinone dimethyl ether, biphenylquinone, thiamethoxam dioxide, etc. azole, Diazoles, triazoles, imidazoles, perylenetetracarboxylic acid, fluorenemethane, anthrones, and their derivatives, metal coordination compounds, and nitrogen-containing five-membered ring derivatives, but not limited to these.

[0107] Examples of the aforementioned metal coordination compounds include lithium 8-hydroxyquinoline, bis(8-hydroxyquinoline)zinc, bis(8-hydroxyquinoline)copper, bis(8-hydroxyquinoline)manganese, tris(8-hydroxyquinoline)aluminum, tris(2-methyl-8-hydroxyquinoline)aluminum, tris(8-hydroxyquinoline)gallium, bis(10-hydroxybenzo[h]quinoline)beryllium, bis(10-hydroxybenzo[h]quinoline)zinc, bis(2-methyl-8-quinoline)gallium chloride, bis(2-methyl-8-quinoline)(o-cresol)gallium, bis(2-methyl-8-quinoline)(1-naphthol)aluminum, and bis(2-methyl-8-quinoline)(2-naphthol)gallium, but are not limited to these.

[0108] The organic light-emitting device according to the present invention can be a bottom-emission device, a top-emission device, or a bidirectional light-emitting device, and in particular, it can be a bottom-emission device that requires relatively high luminous efficiency.

[0109] In addition, the compounds according to the present invention can be included not only in organic light-emitting devices, but also in organic solar cells or organic transistors.

[0110] The manufacture of compounds represented by the above chemical formula 1 and organic light-emitting devices containing them is specifically described in the following examples. However, the following examples are for illustrative purposes only and the scope of the invention is not limited thereto.

[0111] [Manufacturing Example]

[0112] Manufacturing Example 1: Synthesis of Intermediate A

[0113] Step 1) Synthesis of intermediate A-1

[0114]

[0115] Under a nitrogen atmosphere, benzofuran[2,3-b]pyridin-8-ylboronic acid (15.0 g, 70.4 mmol) and 2-bromo-4-chlorobenzaldehyde (17.0 g, 77.5 mmol) were added to tetrahydrofuran (THF, 300 ml), stirred, and refluxed. Then, potassium carbonate (38.9 g, 281.7 mmol) was dissolved in water (117 ml) and added, and after thorough stirring, tetrakis(triphenylphosphine)palladium(0) (2.4 g, 2.1 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated by distillation of the organic layer. The compound was redissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was then distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce intermediate A-1 (14.7 g, 68% yield).

[0116] MS:[M+H] + =309

[0117] Step 2) Synthesis of intermediate A

[0118]

[0119] In a round-bottom flask, intermediate A-1 (20.0 g, 65.0 mmol) and (methoxymethyl)triphenylchloride were added. (methoxymethyl)triphenylphosphonium chloride (24.5 g, 71.5 mmol) was suspended in THF (185 ml) and maintained at 0 °C. Then, potassium tert-butoxcide (8.8 g, 78.0 mmol) was slowly added at 0 °C, and the mixture was stirred at room temperature for 12 hours. After the reaction was complete, distilled water (185 ml) was added for extraction. The extract was concentrated, suspended in dichloromethane (155 ml), dried over anhydrous magnesium sulfate, filtered through silica gel, and concentrated again. The concentrated reaction solution was dissolved in dichloromethane (120 ml), and methanesulfonic acid (6.2 g, 63.7 mmol) was slowly added, and the mixture was stirred at room temperature for 12 hours. After the reaction was complete, the resulting solid was filtered, washed with distilled water (70 ml) and methanol (70 ml), and dried to produce intermediate A (15.0 g, 76% yield).

[0120] MS:[M+H] + =305

[0121] Manufacturing Example 2: Synthesis of Intermediate B

[0122]

[0123] Intermediate B was manufactured by the same method as in Manufacturing Example 1 above, except that 2-bromo-5-chlorobenzaldehyde was used instead of 2-bromo-4-chlorobenzaldehyde.

[0124] MS:[M+H] + =305

[0125] Manufacturing Example 3: Synthesis of Intermediate C

[0126]

[0127] Intermediate C was manufactured by means of the same method as in Manufacturing Example 1 above, except that benzofuran[3,2-b]pyridin-6-ylboronicacid was used instead of benzofuran[2,3-b]pyridin-8-ylboronicacid.

[0128] MS:[M+H] + =305

[0129] Manufacturing Example 4: Synthesis of Intermediate D

[0130]

[0131] Intermediate D was manufactured by the same method as in Manufacturing Example 1 above, except that benzofuran[2,3-c]pyridin-8-ylboronicacid was used instead of benzofuran[2,3-b]pyridin-8-ylboronicacid.

[0132] MS:[M+H] + =305

[0133] Manufacturing Example 5: Synthesis of Intermediate E

[0134]

[0135] Intermediate E was manufactured by the same method as in Manufacturing Example 1 above, except that benzofuran[3,2-c]pyridin-6-ylboronicacid was used instead of benzofuran[2,3-b]pyridin-8-ylboronicacid and 2-bromo-5-chlorobenzaldehyde was used instead of 2-bromo-4-chlorobenzaldehyde.

[0136] MS:[M+H] + =305

[0137] Manufacturing Example 6: Synthesis of Intermediate F

[0138]

[0139] Intermediate F was prepared by means of the same method as described in Manufacturing Example 1 above, except that (6-phenylfuro[2,3-b]pyridin-2-yl)boronic acid was used instead of benzofuro[2,3-b]pyridin-8-ylboronic acid.

[0140] MS:[M+H] + =331

[0141] Manufacturing Example 7: Synthesis of Intermediate G

[0142]

[0143] Intermediate G was manufactured by the same method as in Manufacturing Example 1 above, except that furo[2,3-b]pyridin-2-ylboronic acid was used instead of benzofuran[2,3-b]pyridin-8-ylboronic acid.

[0144] MS:[M+H]+ =255

[0145] [Example]

[0146] Example 1: Synthesis of Compound 1

[0147]

[0148] Under a nitrogen atmosphere, intermediate A (15.0 g, 49.4 mmol) and intermediate a (17.5 g, 54.3 mmol) were added to toluene (300 ml), stirred, and refluxed. Then, sodium tert-butoxide (7.1 g, 74.1 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.8 g, 1.5 mmol) were added. After reacting for 6 hours, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, followed by distillation. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, and then purified by sublimation to produce compound 1 (9.9 g, 34% yield).

[0149] MS:[M+H] + =590

[0150] Example 2: Synthesis of Compound 2

[0151]

[0152] Compound 2 was manufactured using the same method as in Example 1 above, except that intermediate B was used instead of intermediate A and intermediate b was used instead of intermediate a.

[0153] MS:[M+H] + =604

[0154] Example 3: Synthesis of Compound 3

[0155]

[0156] Compound 3 was manufactured using the same method as in Example 1 above, except that intermediate C was used instead of intermediate A and intermediate c was used instead of intermediate a.

[0157] MS:[M+H] + =618

[0158] Example 4: Synthesis of Compound 4

[0159]

[0160] Compound 4 was manufactured using the same method as in Example 1 above, except that intermediate D was used instead of intermediate A and intermediate d was used instead of intermediate a.

[0161] MS:[M+H] + =620

[0162] Example 5: Synthesis of Compound 5

[0163]

[0164] Compound 5 was manufactured using the same method as in Example 1 above, except that intermediate E was used instead of intermediate A and intermediate e was used instead of intermediate a.

[0165] MS:[M+H] + =564

[0166] Example 6: Synthesis of Compound 6

[0167]

[0168] Compound 6 was manufactured using the same method as in Example 1 above, except that intermediate F was used instead of intermediate A and intermediate f was used instead of intermediate a.

[0169] MS:[M+H] + =590

[0170] Example 7: Synthesis of Compound 7

[0171]

[0172] Under a nitrogen atmosphere, intermediate G (15.0 g, 59.1 mmol) and intermediate g (28.7 g, 65 mmol) were added to THF (300 ml) and stirred and refluxed. Then, potassium carbonate (32.7 g, 236.5 mmol) was dissolved in water (98 ml) and added, and after thorough stirring, tetrakis(triphenylphosphine)palladium(0) (2.0 g, 1.8 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, and then purified by sublimation to produce compound 7 (12.4 g, 34% yield).

[0173] MS:[M+H] + =616

[0174] [Experimental Example]

[0175] Experimental Example 1-1

[0176] A glass substrate coated with an ITO (Indium Tin Oxide) film at a thickness of 1400 Å was immersed in distilled water containing detergent and ultrasonically washed. The detergent used was Fischer Co.'s Decon™ CON705, and the distilled water was filtered twice using a 0.22 μm sterilizing filter manufactured by Millipore Co. After washing the ITO for 30 minutes, the ultrasonic washing was repeated twice with distilled water for 10 minutes each. Following the distilled water washing, the substrate was ultrasonically washed for 10 minutes each with isopropanol, acetone, and methanol, and then dried before being transferred to a plasma cleaner. Additionally, the substrate was cleaned with oxygen plasma for 5 minutes before being transferred to a vacuum evaporation machine.

[0177] On the prepared ITO transparent electrode, hole injection layers are formed by sequentially performing thermal vacuum evaporation of HI-A and LG-101 to thicknesses of 800 Å and 50 Å, respectively. On the hole injection layer, HT-A is vacuum-deposited to a thickness of 800 Å as a hole transport layer, and EB-A is vacuum-deposited to a thickness of 600 Å as an electron blocking layer. A mixture of nRH-A and the aforementioned compound 1 in a 1:1 weight ratio is used as the light-emitting layer substrate, and RD-A is used as the dopant. The substrate and dopant are vacuum-deposited to a thickness of 400 Å at a weight ratio of 98:2. Next, as the electron transport and injection layer, ET-A and Liq are vacuum-deposited to a thickness of 360 Å in a 1:1 ratio, followed by vacuum evaporation of Liq to a thickness of 5 Å.

[0178]

[0179] On the aforementioned electron transport and injection layer, magnesium and silver were sequentially deposited in a 10:1 ratio with a thickness of 220 Å; aluminum was then deposited with a thickness of 1000 Å to form a cathode, thereby fabricating an organic light-emitting device.

[0180] Experimental Examples 1-2 to 1-7

[0181] Organic light-emitting devices were manufactured using the compounds listed in Table 1 below instead of compound 1, except that the method was the same as that used in Experimental Example 1-1 above.

[0182] Comparative Experiments 1-1 to 1-3

[0183] Organic light-emitting devices were fabricated using the compounds listed in Table 1 below instead of compound 1, except that the method was the same as in Experimental Example 1-1 above. Compounds H1 to H3 used in Table 1 are shown below.

[0184]

[0185] The organic light-emitting devices fabricated in Experimental Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-3 were subjected to current, and their voltage, efficiency, and lifetime were measured. The results are shown in Table 1 below. In this case, voltage and efficiency were measured by applying a current of 10 mA / cm². 2 The value is determined by the current density; LT97 indicates a current density of 20 mA / cm². 2 The time required for the initial brightness to decrease to 97% at a given current density. When a mixture of two compounds is used as the host, the weight ratio between the host compounds is indicated in parentheses.

[0186] [Table 1]

[0187]

[0188] Experimental Example 2-1

[0189] A glass substrate coated with an ITO (indium tin oxide) film at a thickness of 1400 Å was immersed in distilled water containing detergent and ultrasonically washed. The detergent used was Decon™ CON705 from Fischer Semiconductor, and the distilled water was filtered twice using a 0.22 μm sterile filter manufactured by Millipore. After washing the ITO for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes each. After distilled water washing, the substrate was ultrasonically washed for 10 minutes each with isopropanol, acetone, and methanol, respectively, and then dried before being transferred to a plasma cleaner. Additionally, the substrate was cleaned with oxygen plasma for 5 minutes before being transferred to a vacuum evaporation machine.

[0190] On the prepared ITO transparent electrode, HI-A and LG-101 were sequentially thermally vacuum-deposited to a thickness of 800 Å and 50 Å, respectively, to form a hole injection layer. On the hole injection layer, HT-A was vacuum-deposited to a thickness of 800 Å as a hole transport layer, and compound 1 was thermally vacuum-deposited to a thickness of 600 Å as an electron blocking layer. RH-A was used as the host of the light-emitting layer, and RD-A was used as the dopant. The host and dopant were vacuum-deposited at a weight ratio of 98:2 to a thickness of 400 Å. Next, ET-A and Liq were thermally vacuum-deposited to a thickness of 360 Å in a 1:1 ratio as an electron transport and injection layer, followed by Liq vacuum-deposited to a thickness of 5 Å.

[0191]

[0192] On the aforementioned electron transport and injection layer, magnesium and silver were sequentially deposited in a 10:1 ratio with a thickness of 220 Å; aluminum was then deposited with a thickness of 1000 Å to form a cathode, thereby fabricating an organic light-emitting device.

[0193] Experimental Examples 2-2 to 2-7

[0194] Organic light-emitting devices were manufactured using the compounds listed in Table 2 below instead of compound 1, except that the method was the same as that used in Experimental Example 2-1 above.

[0195] Comparative Experiment Example 2-1 Comparative Experiment Example 2-3

[0196] Organic light-emitting devices were manufactured using the compounds listed in Table 2 below instead of compound 1, except that the method was the same as that used in Experimental Example 2-1 above.

[0197] The organic light-emitting devices fabricated in Experimental Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-3 were subjected to current, and their voltage, efficiency, and lifetime were measured. The results are shown in Table 2 below. In this case, the voltage and efficiency were measured when an applied current of 10 mA / cm² was applied. 2 The value is determined by the current density; LT97 indicates a current density of 20 mA / cm². 2 The time required for the initial brightness to decrease to 97% at a given current density.

[0198] [Table 2]

[0199]

[0200] As can be seen from the results in Tables 1 and 2 above, when compounds with the structure of chemical formula 1 are applied to organic electroluminescent devices, devices with characteristics of low voltage, high efficiency, and long lifespan can be obtained.

[0201] [Symbol Explanation]

[0202] 1: Substrate 2: Anode

[0203] 3: Light-emitting layer 4: Cathode

[0204] 5: Hole injection layer; 6: Hole transport layer

[0205] 7: Electron blocking layer; 8: Electron transport and injection layer.

Claims

1. A compound represented by the following chemical formula 1: Chemical Formula 1 In the chemical formula 1, A is a benzene or naphthalene ring fused with an adjacent ring. L1 to L3 are each independently C that is directly bonded, substituted, or unsubstituted. 6-20 Alpha-aryl Ar1 and Ar2 are each independently phenyl, biphenyl, naphthyl, dibenzofuranyl, or dibenzothiopheneyl. Y is either O or S. X1 to X4 are each independently N or CR2, and any one of X1 to X4 is N. R1 and R2 are each independently hydrogen; deuterium; or substituted or unsubstituted C. 6-20 Aryl, When A is a benzene ring, n is an integer from 1 to 5; when A is a naphthalene ring, n is an integer from 1 to 7. The term "substituted or unsubstituted" refers to being substituted by one or more deuterium atoms or not being substituted.

2. The compound according to claim 1, wherein, The chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-4: Chemical Formula 1-1 Chemical formula 1-2 Chemical formulas 1-3 Chemical formulas 1-4 In the chemical formulas 1-1 to 1-4, L1 to L3, Ar1, Ar2, Y, and X1 to X4 are the same as defined in claim 1.

3. The compound according to claim 1, wherein, L1 to L3 are each independently directly bonded, phenylene, or biphenyl dimethyl.

4. The compound according to claim 1, wherein, R1 can be either hydrogen or deuterium independently. R2 can be hydrogen, deuterium, or phenyl independently.

5. The compound according to claim 1, wherein, The compound represented by the chemical formula 1 is selected from any one of the following compounds: 。 6. An organic light-emitting device, wherein, include: A first electrode, a second electrode disposed opposite to the first electrode, and an organic layer of one or more layers disposed between the first electrode and the second electrode, wherein one or more of the organic layers comprises the compound according to any one of claims 1 to 5.

7. The organic light-emitting device according to claim 6, wherein, The organic layer is either a light-emitting layer or an electron-blocking layer.

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